Anthraquinone dyes and their production



United States Patent Claims. 01. zen-247.5

The present invention relates to new blue dyes having the generalformula:

in which the radical R denotes an alkyl, aryl or a-lkoxyl group or anamino group bearing one or two hydroxyalkyl or alkoxylalkyl radicals assubstituents; the radical R denotes a hydrogen atom, an alkyl group, analkoxyalkyl group or a hydroxyalky-l group; the radical R denotes ahydrogen atom, an alkyl group, an alkoxyalkyl group or a hydroxyalkylgroup or R and R together with the amino nitrogen atom may be commonmembers of a heterocyclic ring and the ring A may bear halogen atoms,alkyl groups, alkoxy groups, hydroxyl groups, carbomethoxy groups,alkylsulfone groups or substituted sulfonamide groups as substituents.The invention also relates to a method of preparing the said dyes.

The new dyes are eminently suitable for dyeing and printing linearpolyester and polyamide materials. They have high substantivity fortextile materials of the said substances and fulfil the requirements asregards extremely high thermal fastness properties.

The new dyes are obtained when azine chlorides having the generalformula N \N o HN(HJ (L01 II I AG N i COR n l 0 NI-n (II) in which theradical R and the ring A have the above meanings are reacted by aconventional method with amadvantageous to use a large excess of amine,for example monia or a primary or secondary amine having the generalformula:

Ra Hr R (III) in which the radicals R and R have the above meanings.

The azine chlorides having the general Formula II to be used as initialmaterials are known from German patent specification No. 1,073,130 andmay be obtained by the general method of production given in the saidpatent specification from a phenyldichlorotriazine and a1,4-diaminoanthraquinone derivative which bears an acyl radical in2-position.

The phenyldichlorotriazine may bear halogen atoms, hydroxyl groups,alkyl groups, such as methyl groups or ethyl groups, alkoxy groups, suchas methoxyl groups, carbomethoxy groups or substituted sulfonamidegroups, such as dimethylsulfonamide or di-(hydroxyethyl)-sulfonamidegroups, in the phenyl radical. Examples of 1,4-diaminoanthraquinonederivatives which hear an acyl radical in 2-position are those havingthe acyl radicals COCH COC H Reaction of the azine chlorides having thegeneral Formula II with amines having the general Formula III isadvantageously carried out in an inert organic solvent at 50 to 250 0,preferably at to C. Examples of suitable solvents are o-dichlorobenzene,trichlorobenzene, nitrobenzene and N-methylpyrrolidone. It is 2 moles ofamine to 1 mole of azine chloride, in order to bind the hydrogenchloride formed; the reaction may also take place in the amine assolvent. It is also possible to add separately a tertiary amine, forexample triethylamine, or a sterically hindered secondary amine, forexample diisopropylamine, to bind the liberated hydrogen chloride.

Dyes according to this invention dye materials, such as textilematerials, of linear polyesters either by the high temperature method orby the thermosol method, and of polyamide, advantageously in thepresence of small amounts of a carrier, for example a product obtainableby reaction of 1 mole of castor oil with 40 moles of ethylene oxide, inblue shades having high fastness properties. These dyeings aredistinguished by good light fastness and wash fastness and by extremelyhigh heat setting fastness.

The following examples will further illustrate the invention. The partsspecified in the examples are parts by weight.

Example I A mixture of 23.5 parts of 2-chloro-4-phenyl-6-[1-amino-2-acetylanthraquinonyl-(4)] aminotriazine (1,3, 5), 10.5 parts ofdiethanolamine and 100 parts of nitrobenzene is stirred for five hoursat 150 C. The reaction mixture is cooled to 100 C. and the nitrobenzeneis distilled off with steam. The resultant precipitate is suctionfiltered, washed with water and dried. 23 parts of the dye having theformula:

II2N is obtained; it dyes polyester textile material fast blue shades bythe high temperature method (135 C., acetic acid).

Example 2 23.5 parts of2-chloro-4-m-tolyl-6-[l-amino-Z-acetylanthraquinonyl-(4)]-aminotriazine-(1,3,5)is reacted in 200 parts of nitrobenzene with parts of'y-methoxypropylamine as described in Example 1. The product is dried.23 parts of the dye having the formula:

0 I H COC- I NHz If is obtained; it dyes polyester textile material fastblu shades by the thermosol method.

Example 3 23.5 parts of2-chloro-4-phenyl-6-[l-amino-Z-acetylanthraquinonyl-(t)]-aminotriazine-(l,3,5) is reacted in 4 300 parts of nitrobenzene with9 parts of morpholine for three hours at 150 C. The reaction mixture isprocessed as described in Example 1, and dried. 26 parts of the dyehaving the formula:

l I-NH O Example 4 A mixture of 10 parts of2-chloro-4-phenyl-6-[l-amino- 2 carbomethoxyanthraquinonyl (4)]aminotriazine- (1,3,5), 6 parts of diethanolamine and 70 parts ofnitrobenzene is stirred for three hours at 150 C. The nitrobenzene isdistilled off with steam, and the dye is suction filtered, Washed withmethanol and dried. 9 parts of the dye having the formula:

is obtained; it dyes polyamide textile material fast blue shades.

Example 5 A mixture of 23.5 parts of2-chloro-4-phenyl-6-[lamino-2-acetylanthraquinonyl (4)] aminotriazine(l, 3,5), 12 parts of diethanolamine and 100 parts of nitrobenzene isheated for five hours at C. The reaction mixture is worked up asdescribed in Example 1. 23 parts of the dye described in Example 1 isobtained.

We claim:

1. A dye having the formula N N (I) HNlN Y X Y I O NH wherein X is amember selected from the group consist- 3. The dye having the formulaing of -COCH COOCH --COC H -CO-CH CH OCH CO-NHCH CH OH CONHCH CH CH OCHCON(OH CH ---OH) Z is a member selected from the group consisting ofhyand drogen, halogen, methyl, ethyl, methoxyl, carbomethyl,dimethylsulfonamido and di-(hydroxyethyl)-sulfonamido and Y is a memberselected from the group consisting of -N N --N \CHPCHPOH CH3 @2115 I NHO (Hiram-0H CHr-CHrCHz-OH CHrOHrOH CHPOHrOHFOH O l CH3 HaCOO Q A OCH, I5. The dye having the formula /OH2CH2 /CH2H2 -HN -N I N 0H2 GHQ-CH2GHQ-0H1 CHn-CH: GHQ-0H2 GHr-CH: N O, N 8 and --N 802 om-ofii oHz-oE,0112-011: E i J 2. The dye having the formula 1 HOOHaCHg Q 60 gw H2 61100111031 1 References Cited by the Examiner /N-kN)l| IH UNITED STATESPATENTS H0CH2CH2 1,437,783 12/ 1922 Steinbach et a1 260-249 I 3,079,3892/1963 Kern et al. 260-249 11300 WALTER A. MODANCE, Primary Examiner.

HzN JOHN M. FORD, Assistant Examiner.

1. A DYE HAVING THE FORMULA